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  • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
  • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
• • H—ELECTRICITY
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  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
  • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
  • H01L31/0352—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions
  • H01L31/035236—Superlattices; Multiple quantum well structures
  • H01L31/035254—Superlattices; Multiple quantum well structures including, apart from doping materials or other impurities, only elements of Group IV of the Periodic System, e.g. Si-SiGe superlattices
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  • H01L31/02—Details
  • H01L31/0236—Special surface textures
  • H01L31/02363—Special surface textures of the semiconductor body itself, e.g. textured active layers
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  • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
  • H01L31/0352—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions
  • H01L31/035209—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions comprising a quantum structures
  • H01L31/035227—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions comprising a quantum structures the quantum structure being quantum wires, or nanorods
• • H—ELECTRICITY
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  • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
  • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
  • H01L31/0352—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions
  • H01L31/035272—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions characterised by at least one potential jump barrier or surface barrier
  • H01L31/035281—Shape of the body
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
  • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
  • H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier
  • H01L31/068—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN homojunction type, e.g. bulk silicon PN homojunction solar cells or thin film polycrystalline silicon PN homojunction solar cells
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E10/00—Energy generation through renewable energy sources
  • Y02E10/50—Photovoltaic [PV] energy

Definitions

• Photovoltaic cells are a major technology for generating electricity which is being deployed ever more widely. Improvements in the efficiency and cost of such cells are important.
• a solar cell requires an internal bias. Usually this internal bias is created by a p-n junction, which is obtained by doping the material. However, doping the material increases the concentration of free carriers and thus increases free carrier absorption and shifts this absorption to higher energies. In addition, increasing the doping increases the bulk recombination rate thus decreasing the conversion efficiency. Reasonably high doping levels are needed to keep sheet resistance low. Therefore, solar cells are often designed to have a very shallow and highly doped emitter region so that the sheet resistance is low and the free carrier absorption and the average bulk recombination rates are small, but this approach limits the thickness of the depletion region and hence how much current light can create in the device.
• Nanomaterials Materials with dimensions smaller than the free carrier diffusion length (nanomaterials) have suppressed free carrier absorption. (See, e.g., reference (2) below.) In this respect nanomaterials would be ideal for solar cells. In addition, nanomaterials have increased absorption and low reflection, which is also ideal for solar cells. However, a solar cell needs a conductive path for the free carriers to travel to the junction. In nanoparticles, a type of nanomaterial with dimensions reduced in all three directions, carriers need to hop or tunnel from one particle to the next. Since hopping and tunneling are inefficient, a highly resistive processes, nanoparticles are non-ideal for solar applications.
• nanowires where dimensions are reduced in only two directions, retain the advantage of suppressed free carrier absorption for light with an electric field perpendicular to the wire axis, while allowing low-resistance transport parallel to the wire axis.
• the nanowires are not in electrical contact with the bulk silicon, not doped, and not aligned.
• the observed efficiency gain in these structures is possibly because the nanowires act like an anti-reflection coating for the bulk cell. Since the nanowires are not vertical to the substrate and not in electrical contact with the substrate, the maximum benefit from nanowires is not realized.
• a photovoltaic device comprises at least two electrical contacts, p type dopants and n type dopants. It also comprises a bulk region and nanowires in an aligned array which contact the bulk region. All nanowires in the array have one predominant type of dopant, n or p, and at least a portion of the bulk region also comprises that predominant type of dopant. The portion of the bulk region comprising the predominant type of dopant typically contacts the nanowire array. The photovoltaic devices' p-n junction would then be found in the bulk region. The photovoltaic devices would commonly comprise silicon.
• a device comprising two or more contacts, a nanostructure partially covering a substrate, and a thin film covering portions of the substrate not covered by the nanostructure but within the nanostructure, wherein the thin film serves as a contact for the device.
• FIG. 1 schematically depicts a solar cell with nanowires atop the cell
• FIG. 2 (prior art) schematically depicts a solar cell with nanowires with concentric p and n regions.
• FIG. 3 (prior art) schematically depicts a solar cell with nanowires comprising both p and n regions.
• FIG. 4 schematically depicts a solar cell with nanowires where the p-n junction lies at the contact of the nanowires and the bulk region.
• FIG. 5 schematically depicts a solar cell with nanowires where the p-n junction lies within the bulk region.
• FIG. 6 schematically depicts a solar cell with nanowires where metal particles are found where the nanowires meet the bulk region.
• FIG. 7 schematically depicts with possible dimensions a silicon nanowire photovoltaic cell with a submerged contact.
• FIG. 8 depicts the dopant profiles expected to result from the diffusion drive-in process recited below.
• a photovoltaic device comprises at least two electrical contacts, p type dopants and n type dopants. It also comprises a bulk region and nanowires in an aligned array which contact the bulk region. All nanowires in the array have one predominant type of dopant, n or p, and at least a portion of the bulk region also comprises that predominant type of dopant. The portion of the bulk region comprising the predominant type of dopant typically contacts the nanowire array. The photovoltaic devices' p-n junction would then be found in the bulk region. The photovoltaic devices would commonly comprise silicon.
• a nanowire based solar cell where the nanowires do not extend all the way to the junction. Instead, the junction is in the bulk region and the nanowires are part of the top part of the junction, as depicted schematically in
• FIG. 5 is a diagrammatic representation of FIG. 5.
• a process for manufacturing solar cells comprising nanowire arrays in which there is a p-n junction in the bulk of the solar cell and the nanowires are part of the emitter.
• Solar cells of the invention may be designed to make use of the suppresion of photocarrier recombination relative to a nanowire solar cell where the nanowires overlap with the depletion region. Nanowires also have a suppressed free carrier optical absorption which decreases the reflection in the nanowires over bulk material.
• the recombination of carriers in our solar cell design may be, for example, about 10 2 , about 10 3 , or about 10 4 less relative to solar cell designs where the nanowires contain or overlap with the depletion region.
• the nanowires are desirably short enough to allow electron and holes created by the light to diffuse through the quasi-neutral region and go into the depletion region.
• the nanowires may be placed outside the depletion region.
• the nanowire array base should be just outside of the depletion region.
• self-aligned metal nanoparticles or films may be produced at the bottom of the nanowire array, as schematically depicted in FIG.
• Plasmonic photovoltaic enhancement is a proposal which is expected to increase the light absorption of a solar cell.
• the surface plasmons of metal particles or thin films placed near a solar cell junction enhance absorption of light near each particle or thin film and hence increase the efficiency of the solar cell, as discussed in reference (5) below.
• incident light is absorbed by the metal nanoparticles or thin film, which transfer energy into the semiconductor by surface plasmon polaritons. An electron and a hole are then created inside the semiconductor via the surface plasmon polaritons.
• the metal at the bottom of the nanowire array can be used as a contact for the device. This would provide a "submerged" contact that directly contacts the full device yet does not significantly block light from being converted into electricity.
• Light is incident onto the cell and partly absorbed in the nanowires, resulting in electron-hole pairs.
• the minority carrier electrons in the nanowires then diffuse to the depletion region and find their way to the backside contact. Some of the light may still be absorbed in the bulk (not nanostructured) p-type region as well as the n-type region, also contributing to current. Photons absorbed in the n-type region also create electron-hole pairs.
• the minority carrier holes diffuse to the depletion region and drift through this region, exiting it by passing to the p-type silicon.
• the carriers then diffuse to the submerged contact to produce current.
• This design allows the light absorption to occur over the full top surface, allows carriers to move to the contacts, and gives a very low contact resistance.
• the nanowire array may have, for example, a height between about 0.05 ⁇ m and about 6 ⁇ m, or between about 0.1 ⁇ m and about 2.5 ⁇ m, or between about 0.5 ⁇ m and about 2 ⁇ m, or between about 1 ⁇ m and about 1.5 ⁇ m, as measured from the substrate.
• the substrate may have a thickness before etching which is highly variable, since it may be, for example, a commercially available silicon wafer or it may be a substrate grown or deposited on a different substrate.
• the substrate from which the nanowires are etched may be as thick as about 1 mm, or 800 ⁇ m, or 500 ⁇ m, down to about 10 ⁇ m, about 6 ⁇ m, or about 3 ⁇ m.
• nanowires of the devices of the invention might have a constant diameter along their length, alternatively they might also have a modest taper. Desirable taper angles might be, for example, no more than about 0.5 degrees, about 1 degree, about 2 degrees, or about 4 degrees, or in a range between about 0.5 degrees and about 1 degree, about 2 degrees, or about 4 degrees.
• the nanowires may be exactly or approximately perpendicular to their substrate.
• the nanowires' deviation from perpendicularity might, for example, be no more than about 0.5 degrees, about 1 degree, about 2 degrees, or about 4 degrees, or in a range between about 0.5 degrees and about 1 degree, about 2 degrees, or about 4 degrees. Greater deviations from perpendicularity are however also possible.
• junction depth of the devices of the invention may have a fairly wide variation. Measured from the bottom of the nanowires after they are fabricated, it may range from about 30 nm to about 3 ⁇ m, from 300 ran to about 2 ⁇ m, or about 1 ⁇ m to about 1.5 ⁇ m.
• the junction depth may be controlled by the choice of processing conditions with diffusion or ion implantation, for example as discussed in Franssila, reference (20), chapters 14 and 15. Typical processing conditions used for junction depth control would be, for example, the energy of the implanted ions and the duration and temperature of a drive-in period for the dopants.
• dopants are known in the art, for example P, As, B, Sb, Al, Ga, Cu, In, Au, Fe, or Zn.
• the dopants are present at levels chosen as described in the Background to achieve adequate conductivity without unduly raising recombination and free carrier absorption, so that the photoexcited carriers exit the nanowire array and enter into the depletion region before recombining.
• Dopant maximum concentrations may be for example between about 10 ls cm “3 and 10 18 cm "3 , or between about
• a figure of merit affected by the dopant concentration is the diffusion length of the majority and minority carriers. As noted, this diffusion length is strongly affected by the dopant concentration.
• the minority carrier diffusion length is desirably greater than the nanowire length. It may be for example at least about 0.5 ⁇ m, at least about 1 ⁇ m, at least about 2 ⁇ m, at least about 4 ⁇ m, at least about 6 ⁇ m, at least about 10 ⁇ m, or at least about 25 ⁇ m.
• the metal layer in the devices of the invention may have a variety of thicknesses.
• It may lie, for example, between about 10 and about 80 nm, or between about 20 and about
• a nanowire array with a submerged contact has potential uses beyond photovoltaic cells.
• a light emitting diode could be envisioned having the same general structure.
• the back contact and submerged contact would be used to drive a current which would generate photons.
• nanostructures which have forms other than nanowires with processes like those described here. This could be done, for example, by not using nanoparticles underneath the silver or other metal, but rather patterning the silver by some known means (e.g., lithographically) in order to form nanostructures of other forms (e.g., which have elongated cross-sections in a plane parallel to a surface of the bulk region).
• some known means e.g., lithographically
• nanostructures of other forms e.g., which have elongated cross-sections in a plane parallel to a surface of the bulk region.
• the idea of a submerged contact could also be implemented in a similar way with other nanostructuring in place of a nanowire array.
• One acceptable clean is a three step clean. First the substrates are cleaned in solvents using baths of acetone, methanol, IPA, and DI water inside an UltraSonic cleaner. Then the substrate is dried. Lastly, the residual organic materials are cleaned off using a plasma etch where the plasma is oxygen, argon or another suitable type of plasma. BOE (buffered oxide etch) is subsequently used to remove any native oxide formed on the surface.
• nanoparticles e.g., iron oxide, silica
• a continuous layer of silver e.g., 40 run
• physical vapor deposition such as sputtering on top of the substrate to cover both the bare silicon regions and the nanoparticles. It is also useful to Ar clean the surface in-situ prior to metal deposition in order to remove any oxide that might have reformed between BOE and pumping down the chamber.
• H 2 O 2 0.5-30 weight percent H 2 O 2.
• the Ag is in contact with the silicon, the H 2 O 2 oxidizes the silicon, and the HF etches this oxide.
• the Ag contacts the silicon the etch rate is enhanced.
• the silicon will etch everywhere except for where the silver has a hole and at this location a nanowire will form as the silicon is etched around it. The etch is timed so that the nano wires are etched down to the junction, but not through it.
• step 8b) Screen print metal electrodes on the wafers.
• One alternative oxidizer is oxygen, which may be introduced by bubbling oxygen through the HF.
• oxidizers include: ozone, chlorine, iodine, ammonium perchlorate, ammonium permanganate, barium peroxide, bromine, calcium chlorate, calcium hypochlorite, chlorine trifluoride, chromic acid, chromium trioxide (chromic anhydride), peroxides such as hydrogen peroxide, magnesium peroxide, dibenzoyl peroxide and sodium peroxide, dinitrogen trioxide, fluorine, perchloric acid, potassium bromate, potassium chlorate, potassium peroxide, propyl nitrate, sodium chlorate, sodium chlorite, and sodium perchlorate.
• peroxides such as hydrogen peroxide, magnesium peroxide, dibenzoyl peroxide and sodium peroxide, dinitrogen trioxide, fluorine, perchloric acid, potassium bromate, potassium chlorate, potassium peroxide, propyl nitrate, sodium chlorate, sodium chlorite, and sodium perchlorate.
• a process for making photovoltaic cells with submerged contacts could include the following steps.
• Honeywell P854 2:1 Phosphorus by first spinning at 200RPM for 2 sec, followed by a ramp to 3000RPM for 20 sec. There is no need to bake the samples on a hotplate once the SOD has been deposited as would normally be done with photoresist since adequate baking will occur during the drive-in step which follows.
• 850 0 C at a controlled rate of 3°C/min. Once 850 0 C has been reached, the wafers can be removed from the furnace and allowed to cool naturally. The glassy layer left by the SOD is removed by etching in 10wt% HF for 5 minutes.
• the passivation step is turned off and only the etch step is allowed to continue until all the handle silicon is removed, but desirably continues for at least 5 minutes regardless. This is done to remove any C 4 F 8 passivation that may be coating the surface after etching.
• polystyrene spheres have also been used successfully in this process.
• a hydrophilic surface is created on the silicon substrate as described above.
• the polystyrene spheres (purchased from Duke Scientific Corporation) are diluted to a concentration of 1% and spun onto the substrate at 500RPM for 5 seconds followed by a ramp to 2000RPM for 40 seconds.
• the polystyrene spheres create a single monolayer on the surface.
• the Ag alloy can be a multicomponent alloy, not limited to a binary system, made up of a variety of constituents (for example, Pt, Si).
• a portion of the constituents can be of known silicon dopants and types (for example, B, P, As, Sb, Al).
• the dopants can be, for example, less than 1% of the total alloy weight, or less than 0.1% of the total alloy weight.
• the submerged Ag or Ag alloy contact can be heated to a temperature between 25C-900C for a suitable length of time from 0 to 4hrs in order to drive alloy constituents or dopants into the silicon to form a selective emitter.
• the selective emitter will tend to be confined to the areas between the nanowires where the submerged contact exists.
• Al 2 O 3 deposited using ALD (atomic layer deposition), or other materials from other processes can be deposited to coat the submerged contact in order to lower the wetting angle of the submerged contact to keep the metal film intact and prevent it from beading up.
• ALD atomic layer deposition
• season the aqueous HF solution before commencing the etching reaction by flowing O 2 gas into the bath to create a vigorous bubbling for a period of 10 minutes. Once the bath is seasoned, submerge the samples, e.g., for 30 minutes. This may be expected to achieve an average wire length of 1 micron.
• the concentration of HF can vary from full strength (about 49wt%) all the way down to very nominal concentrations. Initial observations have shown that the length of the resulting nanostructure increases as HF concentration is reduced. Concentrations as low as 2 wt% and below may be used. For example, a solution of 8 wt% HF may be used. As the HF concentration is altered, the film thickness may need to be varied for best results. [00078] It may be desirable to ensure that the etch duration and vigorousness are balanced so the contact remains continuous at the base of the nanostructure. A considerable degree of discontinuity, however, is tolerable. The submerged contact may have, for example, no more than about 10 3 , about 10 4 or about 10 5 breaks per cm 2 .
• patent application 20070107103 "Apparatus and methods for manipulating light using nanoscale cometal structures", Krzysztof J. Kempa, Michael J. Naughton, Zhifeng Ren, Jakub A. Rybczynski; (6) G. Goncher, R. Solanki, J.R. Carruthers, J. Conley Jr., Y. Ono, J. Electr. Mat. 35 (7) (2006) 1509-1512; (7) B. Kayes, H. Atwater, N. Lewis, Journal of Applied Physics 97 (2005) 1 14302; (8) U.S. patent application 11/081,967; (9) U.S. Patent application 20070278476; (10) U.S.

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